Substitute Natural Gas from Biomass Gasification

Per Tunå
Department of Chemical Engineering, Lund University, P. O. Box 124, SE-221 00 Lund, Sweden

Worldwide demand for fossil fuels is increasing rapidly and at the same time known
resources are diminishing. Especially energy sources such as oil and natural gas in
Western Europe are almost depleted. This, and the fact that climate changes are more
severe than before, has increased the demand for renewable, clean and sustainable
energy. In Europe, natural gas accounts for about 25% of the total energy distribution
and more energy is distributed as gas than as electricity [1]. It is therefore important to
build up a sustainable gas supply for current and future needs. In this master thesis,
twelve different systems for production of substitute natural gas, SNG, are evaluated.
The systems consists of three gasifiers; entrained-flow, fluidised-bed and indirect and
methanation is evaluated using isothermal and adiabatic methanation. Gas cleanup were
performed using both conventional zinc oxide desulphurisation with PSA upgrade and a
Rectisol® wash. The evaluations were performed through simulations accomplished in
Aspen Plus™.
Methanation Gas upgrading
Introduction Gasification Gas conditioning

SNG
Thermal gasification of biomass is one of many
techniques that can supply the energy needed when
modern society breaks its oil-dependency. The gas
produced from thermal gasification, also known as Biomass Biomass drying
syngas, contains too little methane to be of any
interest and further processing is necessary. Gas Steam generation

upgrading also needs to be applied in order to Power generation

increase the energy density of the gas.
There are a few routes to choose; utilise
methanation reactors to produce methane from the
syngas, produce Fischer-Tropsch (FT) liquids and
methane in FT-reactors or a combination of both.
The H2/CO ratio needs to be set according to
upgrade path with a water-gas shift reactor. Sulphur
is a strong catalyst poison for both methanation and
Fischer-Tropsch catalysts and must be removed.
Regardless of the choice of gas upgrade process, the
syngas must first be cleaned from sulphur, alkali and
other impurities.
Among the gas conditioning techniques
available, a zinc oxide bed for desulphurisation and
pressure swing adsorption, PSA, for gas upgrading
was chosen. To evaluate wet gas conditioning
systems Rectisol® was chosen. The Rectisol®
system handles both desulphurisation and gas
upgrading.
To evaluate all system configurations a simulation
model of the systems will be investigated. The
models are made to evaluate any differences
between the systems, and to some extent, how
different parameters affect the SNG efficiency of the
systems. The systems will comprise water-gas shift
reactor, methanation reactor(s) heat recovery,
desulphurisation, steam generation, drying and gas
Figure 1: Simple flow-diagram of the systems.
upgrading. Figure 1 displays a simple flow-sheet of
the systems.
Several parameters of the system are investigated
by to what extent the effect SNG efficiency
including: PSA methane recovery, isothermal
methanation temperature and system pressure.
Gasification
There are several different gasification
techniques commercially available and they are
usually sorted into two groups; direct and indirect. In
direct gasification the energy required for
gasification is supplied in the same reactor by
oxidising part of the feedstock. Indirect gasifiers
supply energy to the reactions from an external
source such as a burner. Indirect gasifiers are known
to produce gases with higher methane content than
direct gasifiers.
Most gasifiers were however engineered to
gasify coal and as a result not all techniques have a
commercially available full-scale solution for
biomass. Prior to gasification the feedstock needs to
be pre-treated with drying and grinding. The extent
of the pre-treatment depends on the gasifier in use.
 The gasification process is endothermic and thus
requires external heat. Gasification is divided into
two steps; pyrolysis, which is a low temperature
process that operates without any oxidation and
gasification that needs a gasification agent that
contains oxygen such as steam or air [2].
If biomass is heated to about 400°C pyrolysis
will start to occur. The pyrolysis does not require
any oxygen, only the volatile compounds in the
biomass will be gasified. Biomass contains ca 60 %
volatile compounds compared to coal which
contains < 40% volatile compounds. This makes
biomass more reactive than coal. After thermal
decomposition the volatile compounds are released
as H2, CO, CO2, H2O, CH4 etc which is also known
as pyrolysis gas. The remains after the pyrolysis is
char coal [2].
The pyrolysis can not convert all of the biomass
into volatile compounds and therefore gasification is
required. The gasification requires much higher
temperatures than pyrolysis, usually in the range of
800-900°C and with a gasification agent present.
The gasification includes partial oxidation and it
breaks down most of the feedstock into volatile
compounds and the remaining nutrients like alkaline
earth metals etc. end up as ash. The produced gas
from the gasification contains synthesis gas or
syngas which consists of carbon monoxide, CO and
hydrogen, H2. The gas also contains methane, higher
hydrocarbons like ethene, tars and inorganic
impurities like HCL, NH3, H2S and CO2.
There are many types of gasification reactors
including fixed-bed, fluidised-bed and entrained-
flow. The choice of gasifier lies in the gas
composition of the synthesis gas and in the
complexity of system.
Gas conditioning
Production of methane requires carbon monoxide
and hydrogen in the presence of a catalyst. The
H2/CO ratio prior to methanation should be at 3 for
stoichiometric methanation [2]. Of the gasifiers
evaluated in this thesis none produced a gas with a
H2/CO ratio of 3 and a water-gas shift reactor is
necessary.
The water-gas shift reaction is used to shift the
H2/CO ratio of the syngas. The reactors are operated
at either high temperature, HT, or low temperature
LT. There is also a stabilised LT-catalyst that can
operate at temperatures of up to 320°C that is
referred to as medium-temperature shift catalyst.
There are different catalysts for each operating
condition as well as the sulphur contents in the
product gas. The shift reaction (I) is exothermic.
CO + H 2 O ↔ CO 2 + H 2 (I)
There are numerous processes for
desulphurisation and for systems that require a
cleaner gas, the zinc oxide (ZnO) bed can be
utilised. This process operates at 250-300°C and can
remove sulphur down to levels of 100 ppb or even
lower. However, zinc can react with halogens and
form volatile compounds. These must be captured
by a secondary guard bed, which normally consists
of activated aluminium oxide (alumina) [3].
An alternative to zinc oxide beds are wet gas
scrubbing processes. One such system is Rectisol,
developed by Linde and Lurgi, it is able to capture
both sulphur and carbon dioxide. The main
advantage with this process for desulphurisation
compared to zinc oxide is that it can generate a pure
hydrogen sulphide (H2S) stream suitable for a Claus-
plant. The Rectisol process uses sub-cooled
methanol as absorbent and several absorbtion
columns.
Methanation
Methanation or methane synthesis occurs with
reaction (II) which is very exothermic. Due to the
high amount of heat that is released and to the high
concentrations of the reactants, measures have to be
taken to avoid hot-spots and to limit a rise in
temperature. The temperature should also be kept
low to favour the equilibrium [2].
CO + 3H 2 → CH 4 + H 2 O ∆H 0298 = −206kJ/mol (II)
There are several methanation reactor designs
available and this thesis has evaluated isothermal
methanation and adiabatic methanation with
recycled gas. The adiabatic system in use is based on
Haldor Topsoe’s methanation process called
TREMP™ (figure 2), Topsoe’s Recycle Energy-
efficient Methanation Process. The system uses three
adiabatic reactors that utilises product recycle and
intermediate cooling.
Figure 2: TREMP™ methanation process by Haldor
Topsoe [4].
Gas upgrading
For systems using a zinc oxide bed for sulphur
capture a gas upgrade systems needs to be applied to
reach sufficient methane purity in the product gas.
As for sulphur capture, there are numerous systems
available for gas separation and one such system is
pressure swing adsorption or PSA.
 PSA, is based on molecular size separation.
Feeding to the PSA occurs under high pressure and SNG efficiency
large molecules such as carbon monoxide are
0,80
adsorbed to the packing material of the PSA, smaller 0,70 Entrained Flow

Efficiency
passes through the packing. Then the pressure drops, 0,60 gasifier
0,50
Indirect gasifier
thus releasing the adsorbed molecules. A minimum 0,40
0,30
of two adsorber beds are required for continuous 0,20 Fluidised-bed gasifier
operation but PSA units are often composed of four 0,10
0,00
to ten adsorber beds. For PSA’s with clay as packing

Isothermal

Isothermal

Adiabatic

Adiabatic
Rectisol
Rectisol

ZnO
ZnO
material, water must be kept below the dew point
prior to the PSA as it will destroy the packing
material [2]. Hydrogen sulphide adsorbs irreversibly
on the packing and must be removed from the gas
prior to injection [3]. Figure 3: Comparison of SNG efficiencies for the test
systems

Simulation systems
The systems all start after the gasifier, which was
not possible to simulate in Aspen Plus™, and
comprise a water-gas shift reactor, heat recovery,
desulphurisation, methanation followed by gas
upgrading. Biomass drying and steam/oxygen
required for gasification have been included in all
systems. All reactions are assumed to reach
equilibrium. The target production of the plant is
100 MW SNG, based on LHV of methane, which is
approximately 2 kg methane per second. The
pressure for all steam streams is set to 90 bar. All
heat generated in the methanation reactors are used
to generated high pressure steam which is utilised to
produce electricity by means of a steam turbine. The
heat that has to low temperature for high pressure
Efficiency
Results
Figure 3 shows that both the fluidised-bed gasifier
and the indirect gasifier perform better for SNG
production than the entrained-flow gasifier.
Furthermore there are only small differences when
comparing gas upgrading and desulphurisation
systems. But the results would look different if
overall system efficiency were evaluated instead of
SNG efficiency. The Rectisol system has a much
higher power need and lower waste-heat utilisation.
SNG efficiency comparison with/without
methane recovery
0,80 Entrained Flow gasifier

steam, is utilised as district heating along with 0,60 Entrained Flow gasifier with
recovery
condensing steam from the turbines. 0,40 Indirect gasifier

The simulations were performed for the twelve 0,20 Indirect gasifier with recovery
base cases, table 1, with additional simulations to 0,00 Fluidised-bed gasifier
evaluate if system pressure, isothermal methanation
Isothermal

Isothermal

Adiabatic

Adiabatic
Rectisol
Rectisol

ZnO
ZnO

temperature or PSA methane recovery affects the Fluidised-bed gasifier with

recovery
efficiency to SNG. Additional simulations were
performed to evaluate the impact of methane losses
in condensed water. The pressure and temperature Figure 4: Methane recovery impact on SNG efficiency.
simulations where, due to time constraints, only
evaluated for the system containing entrained-flow Recovering methane that is dissolved in water,
gasifier, zinc oxide desulphurisation and isothermal by adiabatic flashing in atmospheric pressure,
methanation. increases the SNG efficiency by 5-10 % depending
on the configuration.
For the following evaluations only the system
Table 1: The twelve base cases between gasifiers and using an entrained-flow gasifier with zinc oxide
methanation/gas cleanup. desulpurisation and PSA gas upgrade were used due
Gasifier Entrained- Fluidised- Indirect to time constraints. But as the results do not differ
flow bed between desulphurisation and gas upgrade systems
Isothermal X X X in the above figures, it should be representative for
methanation/PSA
Isothermal X X X all systems.
methanation/Rectisol Figure 5 show that increasing the system
Adiabatic X X X pressure has a negative impact on the SNG
methanation/PSA efficiency. The reason for the decreased efficiency
Adiabatic X X X
methanation/Rectisol
probably lies in the solubility of methane and to
some extent, carbon monoxide in water at elevated
pressures.
 Efficiency as a function of system pressure Conclusions
0,6
Natural gas is a fossil fuel and as such, will be
0,5 depleted some time in the future. Currently there is a
0,4
good infrastructure for natural gas in Europe and the
SNG efficency

gas grid is expanding. In Sweden the grid is limited

0,3
to the west coast but expansion to Stockholm is
0,2 being evaluated. Therefore, a biomass based
0,1 substitute for natural gas would already have the
0
necessary infrastructure and could phase out natural
0 10 20 30 40 50 60 70 gas over time. Future phase out of SNG in favour of
System pressure (bar(a))
hydrogen is also possible and is planned by E.ON.
Figure 5: SNG efficiency as a function of system The simulations of the systems based on
pressure. different gasification techniques showed that not all
of them are appropriate for SNG production. Indirect
gasification has the advantage of higher methane
SNG Efficiency as a function of methane recovery in the PSA content in the gas leaving the gasifier. The results
0,53 clearly show the advantage of higher methane output
0,52 from the gasifier that both the fluidised-bed and the
0,51 indirect gasifier have. Both gasifiers have
SNG Efficiency

0,5
significantely higher efficiencies than the entrained-
0,49 SNG Efficiency
flow gasifier.
0,48
The choice in gasifier is the most important
0,47
factor as can be seen from the results. Comparing
0,46
results of different systems using the same gasifier,
0,45
90 91 92 93 94 95 96 97 98 99 reveals only small differences, at least when
PSA methane recovery %
evaluating SNG efficiency.
Figure 6: SNG efficiency as a function of PSA methane The simulations show that SNG efficiencies from
recovery. biomass to methane of 50 % are possible with either
gasifier. The fluidised-bed and indirect gasifiers
Increasing the recovery of methane from 90 to 99 %, were able to produce SNG with an efficiency around
according to Volker Eichenlaub [5], increases the 67 %, which coincide with other studies [6].
SNG efficiency by almost 10 % as can be seen in Furthermore, utilising a Rectisol gas cleanup system
figure 6. If a high recovery of methane is possible does not have a significant negative impact on SNG
then it should be implemented as it affects SNG efficiency, but it affects overall efficiency.
efficiency by a significant amount. The only draw The simplest system; zinc oxide desulphurisation
back of a higher recovery is the purity of the and PSA gas cleanup coupled with either
produced gas as it decreases with increased methanation system is the best choice. It is based on
recovery. well established, widely used equipment and it
The isothermal methanation temperature has no offers better efficiency than a wet-gas cleanup such
impact on the SNG efficiency as can be seen in as Rectisol. The only reason for using a Rectisol
figure 7. wash is if there is significant amount of sulphur in
the gas stream for use in a Claus plant or to capture
carbon dioxide. Carbon dioxide capture is not
SNG efficiency as a function of isothermal methanation necessary for biomass based plants as the carbon
temperature
emissions are considered neutral.
0,8

0,75
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0,7
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Received for review March 4, 2008

Citation of this document: Tunå, Per, Substitute Natural Gas from

Biomass Gasification, Synopsis of Master Thesis, March 2008,
Department of Chemical Engineering, Lund University, P. O. Box
124, SE-221 00 Lund, Sweden

Responsible Thesis Advisor: Hans.Karlsson@ChemEng.LTH.se